Dyeing or coloring of products made with cellulose acetate



Patented Aug. 11, 1931 PATENT OFFICE GEORGE HOLLAND ELLIS, OF SPONDON,

NEAR DERBY, ENGLAND, .ASSIGNOR TO CELANESE CORPORATION OF AMERICA, A CORPORATION OF DELAWARE DYEING OR COLORING OF PRODUCTS MADE WITH CELLULOSE' ACETATE No Drawing. Original application filed September 25, 1923, Serial 110.664,?81, a'nd inGreat Britain January 27, 1923. Divided and this application filed December 27, 1926. Serial No. 157,414.

In my Patent 1,618,418 granted Feb. 22,

1927 there is described a process for dyeing, coloring, printing or stencilling yarns, threads, filaments, fabrics, films or other materials consistin of cellulose acetate alone or associate with other fibres or materials.

In the specification of my said U. S. patent, I have proposed to employ for the dyeing, printing or stencilling of such goods ormaterials any organic compounds or coloring matters which are favourably constituted or have an afiinity for cellulose acetate or are capable of dyeing or coloring the same, but which are insoluble, pr-actically insoluble or of relatively low solubility in water, all of which are hereinafter included in the expression relatively Waterinsoluble by employin them in the form of dispersed, i. e. solufile or more soluble modifications obtained by pretreating them withone or more bodies having oily or fatty characteristics containing salt-forming groups capable of forming soluble salts with alkalies or ammonia, for example the sulpho group or the carboxyl group or both sulpho and carboxyl groups, or salts of such bodies such for instance as their sodium or other alkali salts or ammonium salts. Such bodies and their salts are hereinafter, as

' in the said application, included in the term ammonium salts.

body of oily or fatty characteristics.v In particular according to my said U. S. patent one can employ dispersed modifications obtained by treating the said organic compounds or coloring matters with sulphoricinoleic or other sulp'honated fatty acids or salts thereof such as the alkali or Other bodies of oily or fatt characteristics instanced in my said U. S. patent are for example oleic, stearic or palmitic acid and salts thereof such as the alkali and ammonium salts.

The specification of my said U. S. Patent 1,618,413 gives many examples of classes of organic compounds or coloring matters insoluble or of relati-velylow solubility in water which may be applied in dispersed modifications as referred to. Amongst these are indicated unsulphonated or other Wool or other threads or fibres.

insoluble or relatively insoluble compounds or coloring matters of the azo class; unreduced coloring matters of the substituted quinone-monoimide series generally comprised within the term indophenols; coloring matters or compounds of the following classes, usually containing no sulpho groups :diphenylmethane, triphenylmethane, tria'rylmethane, oxazine, azine, diazine, thiazine, unreduced indigoid; basic derivatives of the anthraquinone series; such as aminoanthraquinones, aminohydroxyanthraquinones, or their derivatives such as 1-hydroxy4-paratolylamino-anthraquinone, 1 paratolylamino -4-methylaminoanthraquinone and so forth; or (for employment according to the azoic or develop-- ment method) simple amino bases.

It is further stated in my said U. S. patent that the dispersed modifications of the organic compounds or coloring matters or of the simple amino bases may be employed for the dyeing of mixed materials containing cellulose acetate associated with cotton, silk, Especially it is stated that the dispersed modifications of favourably constituted organic compounds or coloring matters may be applied to the dyeing of goods consisting of cellulose acetate and one or more of the fibres: cotton, wool, silk, artificial silks of the cellulose type, having no afiinity or less aifinity than the cellulose acetate for said dispersed compounds or coloring matters, so that the cellulose acetate is selectively or' preferentially colored thereby, the other fibre, or one or more of the other fibres, being dyed or colored to similar or differential shades relatively to the cellulose acetate by other coloring matters or compounds or the employment of such other coloring matters or compounds being omitted.

It is further stated in my said U. S'. patent; that in dyeing materials consisting of or containing cellulose acetate with the dispersed modifications of any of the insoluble or rela tively low soluble organic compounds or coloring matters having an affinity for cellu-' lose acetate, other dyes may or "may not be employed in combination or association with them in the same operation, or in separate operations, for the production of compound shades on the cellulose acetate.

For further particulars and examples of organic compounds or coloring matters insoluble or of relatively low solubility in water, which may be applied in dispersed modificationsas aforesaid for dyeing goods consisting of or containing cellulose acetate, and as to the manner in which they may be applied, I refer to my said U. S. Patent 1,618,413.

Now U. S. Patent 1,618,414, of which the present is a divisional application, likewise concerns the dyeing of goods such as referred to consisting of or containing cellulose acetate with the aid of dispersed, i. e. soluble or more soluble, modifications of organic compounds or coloring matters having an 'afiinity for or capable of coloring cellulose acetate but insoluble, practically insoluble or of relatively low solubility in Water, all. of which are herein included in the expression relatively water-insoluble.

The said U. S. Patent 1,618,414 states that in any of the cases referred to in thespecification of said Patent 1,618,413 one may employ Wholly or partly instead of the solubilizing agents therein referred to, other organic bodies as dispersing agents for the organic .compounds or coloring matters or simple amino bases to be applied to the materials consisting of or containing cellulose acetate. 1

one or more of any of these groups; or den-Q Such other organic solubilizing agents comprising a wide range of non-oleaginoiis compounds, being organic derivatives-contaimng in their structure. one or more salt forming groups such as the sulphonic, carboxyl, or hydroxyl groups, (whether the compoundcontains only one kind of these groupsor different kinds of these groups at -the same time) and salts of such bodies; for example one mayemploy phenols, sulphonic acids, carboxylic acids, phenolsulphonic acids or other derivatives of .the benzene, naphthalene or anthracene series, containing vatives of other cyclic hydrocarbons, saturated or non-saturated, containing one or more of the above mentioned groups, such for exampleasthe naphthenic acids, naph-. thene sulphonic acids or-other carboxylic or sulphonic acids of the cyclo may employ the sodium or ot er salts of one or more of any of the above mentioned dee rivatives. All such ,organic salt forming derivatives as aforesaid and their salts are hereinafter included in the expression carboc clic dispersing nt.

basic derivatives of the an I, uimne series,

ow the present divisional application such as aminoanthraguindnes,aminohydroxyanthraquinones, or their derivatives, such as l hydroxy 4 paratolylaminoanthraquinone, 1 paratolylamino 4 methylaminoanthraquinone and soforth.

The dispersed modifications thereof may be made by merely grinding or mixing the dispersing agent or mixtures of dispersing agents, with the suitable coloring matter, organic compound or simple amino base, etc., or by heating under ordinary atmospheric pressure or under increasedprreduced pressure in the presence or absence of water. The dispersed modifications of the coloring matter or compound or mixtures of; same may then be utilized for an of'the purposes described in the specification ofmy said Patent 1,618,413 for example For the, dyeing of acetyl cellulose, by simply dissolving the dis rsed modification in hot or cold water, tering into the dyebath (which may be acid, neutral or alkazlline) and conducting the dyeing as usu -1 For printing or stencillingnaeetyl cellulose, by thickening, as may required, a solution ofthe dispersed modification, 'or mixture of such, by the use. of substances such' as starches, gums, flour and the like and applying in the usual manner, follows by such after-treatment as may be r uisite;

For the dyeing or print' I containin acetyl cellul either in uniform' sha es or in contr 4 g colors or having the material other than the acetyl cellulose uncolored.

of mixe goods It is further understood? that mixtures, 7

containing difierent. carbocyclic dispersmg agents of the said Patent 1,618,414 maybe employed, or mixtures of-one or more of them with one or more of the solubilizing agents of my said Patent 1,618,413, and that the ex, ression a medium comprising a carychc dispersin agent in the claims is to be read as inclu gany such mixtures as well as the individual carbocyclic dispersing agents themselves.

' (1 ing, printing and stencillin ilhe term com und of the na hthenic acid class in the c aims comprises t e naphthenic acids and naphthene sulphonic acids and their sodium or other salts.

Further the term aminoanthraquinones in the claims is to be understood to include the ant such as 1-hydroxy-4-paratolylaminoanthn quinone, l-paratolylamino-4-methylamineanthraquinon'e and-so forth.

,lfii ilatent is: -V r K ro for and other product con mnuim m tats, comprising applying thereto an sqw m simple'aminoanthraquinone's, aminehydroxyraquinones and their simple derivatives,

What I claim and desiretosecure the dyeingpf yarns, iahrim tie with a carbocyclic dispersing agent. n 2. In and for the dyeing of yarns, fabrics I and-other products comprising cellulose acetate, the employment of relatively waterinsoluble basic derivatives of the anthraquinone series, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a medium comprising a carbocyclic dispersing agent which is a compound .of the class consisting of naphthenic acids and naphthene sulphonic acids and their salts.

3. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble basic derivatives of the anthraquinone series, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a medium comprising a carbocyclic dispersing agent which is a naphthenic acid salt.

4. In and for the dyeing of yarns, fabrics and other products com rising cellulose acetate, the employment of relatively water-in soluble basic derivatives of the anthraquinone series, said compounds being employed in the formof dispersed modificationsobtained by pretreating them with a medium comprising a naphthenic acid sodium salt.

5. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble basic derivatives of the anthraquinone series, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent and a body of oily or fatty characteristics. 6. In and for the dyeing of yarns, fabrics and other products comprlsing cellulose acetate, the employment of relatively. waterinsoluble basic derivatives ofthe anthraquinone series, said compounds bein employed in the form of dispersed modi cations obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent which is a compound of the class consisting of naphthenic acids and naphthene sulhonic acids and their salts and a higher atty acid compound. 1 p

7. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relativel waterinsoluble basic derivatives of the ant raquinone series, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent which is a compound of the class consisting of naphthenic acids and naphthene sulphonic acids and their salts and a sulphonated ricinoleic acid compound.

8. In and for thedyeing of yarns, fabrics and other products comprlsing cellulose acetate, the employment of relatively waterinsoluble basic derivatives of the anthraquinone series, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent which is a na'phthenic acid salt and sodium salt of sulphoricinoleic acid.

9. Process for the dyeing of yarns, fabrics and other products containing cellulose acetate,comprising applying thereto an aque-- ous dispersion of a relatively water-insolu- I ble coloring matter, which is an anthraquinone, the said-dispersion being prepared by a process involving pretreating the coloring matter with a carbocyclic. dispersing agent.

10. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble aminoanthraquinones, said compounds being employed in the form of dispersed modifications obtained ,by" pretreating' them with a medium comprising a carbocyclic dispersing agent which is a compound of the class consisting of naphthenic acids and naphthene sulphonic acids and their salts.

11. In and for the dyein'g of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble aminoanthraquinones, said ,com-

.pounds being employed in the form of dispersed modifications obtained by. pretreating them with a medium comprising a carbocyclic dispersing agent which is a naphthenic acid salt.

12. In and for the dyeing of yarns, fabrics and other products com rising cellulose acetate, the em loyment o relatively water-insoluble amlnoanthraquinones, said compounds being employed in the form of dispersed modifications obtained by pretreating them withalnedium comprising a naphthenic acid sodium salt.

13. In and for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble aminoanthraquinones, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent and a body of.

them with a mixture comprising acarbocyclic dispersing agent which is a compound of the class consisting of naphthenic acids and naphthene sul honic acids and their salts and a higher atty acid compound.

15. Brand for the dyeing of yarns, fabrics and other products comprising cellulose acetate, the employment of relatively waterinsoluble aminoanthraquinones, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent which is a compound of the class consisting of naphthenic acids and na hthene sulphonic acids and their salts and a sulphonated ricinoleic acid compound.

16. In and for the dyeingvof yarns, fabrics and other productscomprising cellulose acetate, the employment of relatively waterinsoluble aminoanthraquinones, said compounds being employed in the form of dispersed modifications obtained by pretreating them with a mixture comprising a carbocyclic dispersing agent which is a. na hthenic acid salt and sodium salt of sulp 0- ricinoleic acid. a In testimony whereof I have hereunto subscribed my name.

GEORGE HOLLAND ELLIS. 

